Noncorrosive fuels and lubricating oils

ABSTRACT

A METHOD OF INHIBITING CORROSION IN HYDROCARBON SYSTEMS WHICH COMPRISES ADDING FROM 0.01-100 P.P.M. OF BIS-1,3-ALKYLAMINO-2/PROPANOL OR PHOSPHORYLATED BIS-1,3ALKYLANINO-2-PROPANOL.

United States Patent Ofice Patented Apr. 4, 1972 3,654,158 NONCORROSIVE FUELS AND LUBRICATING OILS John D. Newkirk, Downers Grove, Ill., assignor to Nalco Chemical Company, Chicago, Ill. No Drawing. Filed Dec. 22, 1969, Ser. No. 887,434 Int. Cl. Cm 1/32, 1/44; C101 N22 US. Cl. 252-493 1 Claim INTRODUCTION In the handling of various organic materials, particularly hydrocarbons and similar organic liquid compositions, it is often necessary to transport and store such materials in metal containers, as in steel, iron or other metal pipelines, drums, tanks and the like. Since these materials often contain varying amounts of water in solution or suspension which may separate, internal corrosion of the container by separating water almost invariably occurs to a greater'or lesser degree. The problem is especially serious when handling gasoline, kerosene, fuel oil, crude oil, etc. In spite of all reasonable and practical precautions during the manufacture of the hydrocarbon distillate, water is found as a film or in minute droplets in the pipelines or in container walls or even in small pools in the bottom of the container. This brings about ideal conditions for corrosion and consequent damage to the metal surfaces of the container. A more serious problem is the contamination of the hydrocarbon oil or other material contained therein by the corrosion products.

Corrosion problems. also occur, for example in the lubrication of internal combustion engines or steam engines including turbines or other similar machinery, in which quantities of water are often observed as a separate phase within the lubricating system as a result of the condensation of water from the atmosphere or, in the case of internal combustion engines, as a result of dispersion or adsorption in lubricating oil of water formed as a product of fuel composition. Water in such instances, corrodes the various metal parts of the machinery with which it comes in contact, the corrosion products causing further mechanical damage to bearing surfaces and the like due to their abrasive nature and catalytically promoting the chemical degradation of the lubricant. Corrosion problems are encountered with other oils including cutting oils, soluble oils, rolling oils, the latter comprising oils used in the rolling of metals which oils may be used in other forming operations such as stamping, cutting, casting, etc., of metals, etc. Those oils may be of mineral, animal or vegetable origin. Corrosion problems also arise in the preparation, transportation, and use of alcohols, ketones, etc. and in various coating compositions such as greases, both of synthetic and petroleum origin, waxes, household oils, paints, lacquers, and many others which are supplied to metal surfaces for protective purposes.

Therefore, in many facilities handling petroleum finished products there is a need to mitigate corrosion. Recently there is new emphasis on the effects of these corrosion inhibitors on the physical characteristics of the finished products or fuels to which they are added. This new emphasis can be largely attributed to the increased need for fuels of higher quality for internal combustion engines and the jet engines. Recent specifications cover solubility and emulsifying properties of the additives. Compositions that do not meet the specifications of solubility in isooctane and emulsifying characteristics are rejected. Further specifications that effective corrosion inhibitors must meet are compatibility, ash, and Water Separomater Index, Military (WSIM) which will be explained later.

Furthermore, in many petroleum processes involving the handling of hydrocarbons, corrosion is a serious problem. Thus, there is a need to protect process equipment from corrosion.

OBJECTS It is an object of this invention to provide a new refinery process corrosion inhibitor. This new corrosion inhibitor should not require extensive processing in its manufacture.

It is a further object of this invention to provide a corrosion inhibitor that meets the specifications required of reigriery process additives, such as. solubility and compati- It is a further object to provide a corrosion inhibitor that is soluble in hydrocarbons.

A further object is to provide inhibitors of this type which will satisfactorily prevent corrosion of certain metal surfaces by water in contact with organic materials and metal surfaces.

Further objects are to provide corrosion inhibitors which are stable at ordinary temperatures of use, easily and inexpensively prepared and which would not deleteriously affect organic materials with which they are incorporated.

Other objects, together with some of the advantages to be derived from utilizing the inhibitors of the present invention, will become apparent from the following detailed description thereof.

THE INVENTION This invention relates to a novel method for inhibiting corrosion of metal surfaces in contact with organic material that contains small amounts of water. This method comprises adding from 0.01-100 p.p.m. by weight of a bis-(1,3-alkyl amino) propan-Z-ol or a phosphorylated bis (1,3-alkyl amino) propan-2-ol to the organic material. The bis-(1,3-alkyl amino) propan-Z-ols, herein referred to as his propanols, is prepared by the reaction of amines with epihalohydrin.

In general, the molar ratio of epihalohydrin compound to amine ranges from about 0.9: 1.5 to 1.0:2.0. Preferably, about one mole of epihalohydrin is reacted with two moles of amine. It is understood that, in some cases, an excess of amine may be supplied to the reaction zone in order to insure complete reaction, the excess being removed subsequently in any suitable manner. When two moles of amine are reacted per mole of epihalohydrin compound,

- the amine may comprise the same or difierent amine anti-static agents, in flotation processes, as carriers and collecting agents, as pesticides, herbicides, and biocides,

and as intermediates for adhesives, pharmaceuticals, dyes,

The preparation of bis-propanols is taught by US. Pat. 3,017,258. R R NH is the amine used and R and R represent similar or different radicals attached to the nitrogen of the amine. Thus a wide variety of amines could be:

Any suitable [primary or secondary] alkyl amine may be used in preparing the additive of the present invention. It is understood that the term alkyl amine is used in the present specifications and claims to include primary alkyl amines, secondary alkyl amines, polyamines, N-alkyl polyamines, N,N'-dialkyl polyamines, etc., all of which meet the requirements hereinbefore set forth. [Any amount of branching is permitted] Illustrative examples of primary alkyl amines include dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, heytadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine, pentocosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine, hentriacontyl amine, dotriacontyl amine, tritriacontyl amine, tetratriacontyl amine, pentatriacontyl amine, hexatriacontyl amine, heptatriacontyl amine, octatricontyl amine, nonatriacontyl amine, tetracontyl amine, etc. Conveniently the long chain amines are prepared from fatty acids or more particularly mixtures of fatty acids formed as products or by-products. Such mixtures are available commercially, generally at lower prices and, as another advantage of the present invention, the mixtures may be used without the necessity of separating individual amines in pure state.

As an example of such a mixture is hydrogenated tallow amine which is available under various trade names including Alamine H26D and Armeen HTD. These products comprise mixtures predominating in alkyl amines containing 16 to 18 carbon atoms per alkyl group, although they contain a small amount of alkyl groups having 14 carbon atoms, and also meet the other requirements hereinbefore set forth. [Tertiary amines cannot be used in the present invention] Illustrative examples of secondary amines include di(dodecyl) amine, di(tridecyl) amine, di(tetradecyl) amine, di(pentadecyl) amine, di(hexadecyl) amine, di (heptadecyl) amine, di(octadecyl) amine, di(nonadecyl) amine, di(eicosyl) amine, etc. [Further] illustrative examples of such compounds include N-propyldodecyl amine, N-butyl-dodecyl amine, N-amyl-dodecyl amine, N-butyl-tridecyl amine, N-amyl-tridecyl amine, etc., N-propyl-tetradecyl amine, N-butyl-tetradecyl amine, N- amyl-tetradecyl amine, etc. Here again, mixtures of secondary amines are available commercially, usually at a lower price, and such mixtures may be used in accordance with the present invention, provided that the amines meet the requirements hereinbefore set forth. An example of such a mixture available commercially is Armeen 2HT which consists primarily of dioctadecyl amine and dihexadecyl amine. [Branched primary or secondary amines can be used such as t-butyl primary amine and toctyl primary amine] Preferred examples of N-alkyl polyamines comprise N-alkyl-1,3-diaminopropanes in which the alkyl group contains at least 12 carbon atoms and a straight chain of at least three carbon atoms attached to the nitrogen atom. Illustrative examples include N-dodecyl-1,3-diaminopropane, N-tridecyl-1,3-diaminopropane, N-tetradecyl-1,3-diaminopropane, N-pentadecyl-1,3-diaminopropane, N-hexadecyl-1,3-diaminopropane, N-heptadecyl-l,3-diaminopropane, N-octadecyl-1,3-diaminopropane,

N-nonadecyl-1,3-diaminopropane, N-eicosyl-l,3-diaminopropane,' N-heneicosyl-1,3-diaminopropane, N-docosyl-l,3-diaminopropane, N-tricosyl-l,3-diaminopropane, N-tetracosyl-1,3-diaminopropane, N-pentacosyl-1,3-diaminopropane, N-hexacosyl-1,3-diaminopropane, N heptacosyl-1,3-diaminopropane, N-octacosyl-1,3-diaminopropane, N-nonacosyl-1,3-diaminop1fopane, N-triacontyl-l,3-diaminopropane', v N-hentriacontyl-1,3-diaminopropane, N-dotriacontyl-l,3-diaminopropane, N-tritriac0ntyll,3-diaminopropane,:. N-tetratriacontyl-1,3-diaminopropane, N-pentatriacontyl-1,3-diarninopropane, N-hexatriacontyl-1,3-diaminopiopane, N-heptatriacontyl-l,3-diaminopropane, N-octatriacontyl-l,S-diaminopropane, N-nonatriacontyl-l,3-diaminopropane, N-tetracontyl-1,3-diaminopropane, etc.

As before, mixtures are available commercially, usually at lower prices, of suitable compounds of this class and advantageously are used for the purposes of the present invention. One such mixture is Duomeen T which is N- tallow-1,3-diaminopropane and predominates in alkyl groups containing from 16 to 18 carbon atoms each, although the mixture contains a small amount of alkyl groups containing 14 carbon atoms each- Another, mixture available commercially is N-coco-l,3-diaminopropane which contains alkyl groups predominating in 12 to 14 carbon atoms each. Still another exampleis Nesoya-lfidiaminopropane which predominates in alkyl groups containing 18 carbon atoms per group, although it contains a small amount of alkyl groups having l6 carbonQatoms."

As hereinbefore set forth, two different amines may be reacted with the epihalohydrin, compound... The amines must meet the qualifications hereinbefore set forth. [In using two different amines, the amine mixture is reacted with the epihalohydrin. This reaction is not a stepwise reaction of one amine and then the second amine but rather a concurrent reaction of both amines with the epihalohydrin.] v i As hereinbefore set forth, the amine compound is reacted with an epihalohydrin compound. Epichlorohydrin is preferred. Another epichlorohydrin compound that could be used is 2,3-epi-4-chlorobutane. [An epihalohydrin such as 1,2-epi-4-chlorobutane,could not be used to produce a product by the mechanism, since the configuration prevents the reformation of the epoxy ring after one mole of the amine is reacted with the epihalohydrin and the caustic is added. Without the reformation of the epoxy ring, the caustic and subsequently the second mole of amine cannot react with the intermediate to form the bis-propanol product. Thus, the space relationship determines whether or not this reaction mechanism can take place and produce the bis-propanol. Any glyceryl chlorohydrin could be used because the epoxy ring can easily be formed] In general, the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be employed. In some cases epidihalohydrin compounds may be utilized. It is under? stood that the different epihalohydrin compounds are not necessarily equivalent in the same or different substrate and that, as hereinbefore set--forth, epichlorohydrin is preferred.

"The desired quantity of alkyl amineand epihalohydrin compounds may be supplied to the reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant step-wise. Thus, usually it is preferred to supply the alkyl amine to the reaction zone and to add the epihalohydrin compound step-wise, with stirring.

When it is desired to react two different alkyl amines with the epihalohydrin compound, the amines are supplied to the reaction zone, the epihalohydrin compound added gradually, and the reaction completed. Generally, it is preferred not to utilize a solvent, but a solvent could be utilized. A solution of the alkyl amine in a solvent and a separate solution of the epihalohydrin compound in a solvent are prepared, and these solutions then are commingled in the manner hereinbefore set forth. A suitable solvent that may be employed could be an alcohol such as 2-propanol. [The reaction temperature varies dependent on the three phases of the reaction. In the initial reaction of the amine and the epihalohydrin, the temperature can range from 1580 C. and preferably ranges from 50-65 C. This reaction step takes from .1 to 2 hours dependent on the temperature and amine used. The temperature generally should not exceed 75 C. Caustic is added and the temperature range is the same. The mixture is heated for l to 2 hours with about 75 C. being the maximum temperature. Before the wash water is added, the temperature .is increased to about 100 C. This higher temperature achieves an easier phase separation] Either before or after removal of the reaction product from the reaction zone, the product is treated to remove halogen, generally in the form of an inorganic halide salt as, for example, the hydrogen halide salt. This may be effected in any suitable manner and generally is accomplished by reacting the product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc., to form the corresponding metal halide. The reaction to form the metal halide generally is etfected under the same conditions as hereinbefore set forth. After this reaction is completed, the metal halide is removed in any suitable manner, including filtering, washing, centrifugal separation, etc. It is understood that the reaction product also is heated sufiiciently to remove alcohol and water and this may be effected either before or after the treatment to remove the inorganic halide.

The reaction products prepared in the above manner are new compositions of matter and possess unexpected properties over related but dififerent compositions of matter of the prior art. Depending upon the reactants and conditions employed, the reaction product generally will comprise a mixture of different compounds, which mixture may include polymeric compounds. Another advan' tage to the present invention is that the mixture of compounds prepared in the above manner may be utilized without the added expense and time of separating a specific compound from the mixture. The reaction products will range from liquids to solids and, when desired, may be prepared as a solution in a suitable solvent for ease of handling and using.

The basic synthesis steps involved in the preparation of the bis-propanols are as follows:

where R is a radical independently selected from the group consisting of hydrogen and hydrocarbons having from l-36 carbon atoms and is alkyl, aryl, alkaryl, alkenyl, acyl, oxyalkyl, S-cyanoethyl, alkylene aziridinyl, heterocyclic, alicyclic, and polyoxyalkenyl.

Stoichiometrically, two moles of amine react with one mole of epichlorohydrin. The final reaction product contains the salt generated during the reformation of the epoxy range. Separation of this undesirable salt is achieved during a multi-water wash of the reaction product.

Following is a brief summary of the manufacturing process of the bis-propanols.

Primary and secondary amines or mixtures thereof may be used. The synthesis procedure involves adding with stirring the epichlorohydrin to the amine, containing 5-15 Wate, at 1580 C. and preferably at 50-65 C. The reaction is exothermic after a short conduction period, otherwise the rate of addition is rapid, consistent with heat withdrawal. The reaction mixture is stirred for approximately 1 to 2 hours after addition of epichlorohydrin is complete, whereupon the addition of 50% caustic is initiated. This addition likewise exothermic, is performed at :fiom l580 C. and preferably 50-65" C. and requires approximately 2 to 4 hours.

When the caustic addition is completed, the reaction mixture is warmed slowly to from 50-120 C., and preferably about 100 C. and held there for one hour. Water is then added to dissolve the sodium chloride that is formed. The reaction is kept at 100 C. After a short mixing period the mixture is allowed to stand at 100 C. until the aqueous phase had separated. This aqueous phase was discarded and the wash step was repeated 4 or 5 times. The organic phase is then dried by applying vacuum. The dried material is filtered while hot through Celite. Yields are approximately 100%.

This washing technique for the removal of the salt can be used when the water insoluble, long chain amines are used. When water soluble, short chain amines are used in the process, the product is recovered by distillation, and the salt residue is discarded. Dilution to formulation levels could be made at any time after the drying step.

To better understand the preparation of the bis-propanols, the following example is given.

EXAMPLE I The process requires a kettle, the main feature of which will permit the direct observation of the aqueous and organic phases during the settling period. Otherwise, any vacuum rigged kettle with an adequate stirrer and a jacket which will permit circulation of cold water and later low pressure steam will be satisfactory. To the clean kettle is added 50 pounds of tap water and 684 pounds of P-123 which is a primary amine having from 10-20 carbon atoms in chain length. This mixture is stirred. One hundred twelve pounds of epichlorohydrin is added at 50 and the reaction mixture is stirred for one hour at 75 C. Then 97 pounds of 50% sodium hydroxide is added during approximately 4 hours at 75 C.

The reaction mixture is slowly heated to 100 and held there for one hour after addition of caustic is completed. To the mixture is added 25-0 pounds of water to dissolve the sodium chloride. The mixture is heated to -100-105 C. with stirring for from 10-15 minutes. Stirring is discontinued and the phases are allowed to separate. The lower aqueous phase is withdrawn and discarded. This Washing cycle is repeated four times at with adequate mixing each time to extract the salts. After withdrawal of the final aqueous phase, which should be cut close enough at the expense of a small amount of interfacial material, the aqueous phase is dried under vacuum. The product is filtered through Celite while hot. A temperature of 75-80 has proven satisfactory in laboratory preparations. On cooling to room temperature the 100% active material is a semi-soft wax. The product may be diluted in any concentration with standard hydrocarbon solvents after the washing and drying cycles have been completed either before or after the filtration step if a dilute product is desired.

The following table shows a number of bis-propanols prepared according to the same procedure as set forth in Example I except that the ratio of reactants (moles of epichlorohydrin to moles of amine) varies according to column 3 of the table. Column 2 identifies the specific amine used to make the bis-propanol.

TABLE I [Temperature 180 F., pH 1.8]

Moles EPI: amine reaction ratio hkluu; 6 Dimethyl 7 IYIHz :2

CH;(CH7)4CHCH1 8 IIIHQ CH;(CH2)uCH-CH;

CH;(CH:)1CHCH:

C 1( 2)11C -C 11 Hydrogenated taliow armene HDT" 1:2 12--. Straight chain amine of 16 carbon atoms 1:2 13 Straight chain primary amine Can-C 1:2 14 Dicoco amine 1:2

15 I-|IH 1:

CH3(CH1)12CH-CH3 16 Same as above 17.-. do 18 Primary O11 annne. 19 Mixture 10 and 13 20. Mixture 10 and primary fatty a from coco ami Mixture 12 and secondary Cir amine- 21 22 2-ethy1 hexyl Corrosion inhibiting characteristics Percent protection at Corrosion rate'at dosage,

dosage MPY WSI at 0 5 10 25 0 5 10 25 p.p.m.

30 23 so 37 23 a9 R.P.= Reaction Product. This compound is a corrosion inhibitor used for purposes of comparison. 1 "Armene HDT is a mixture of amines and a hydrogenated tallow amine having alkyl groups of predominantly 16 to 18 carbon atoms.

The table also shows the results of testing the various products as corrosion inhibitors and water separation characteristics, which tests are discussed subsequently.

WATER SEPARATION INDEX, MILITARY The water separation test measures the water separation characteristics of fuels and fuel-additive combinations in terms of an index. This method of test was developed on the basis of cooperative work carried out by the Coordinating Research Council and published in CRC Report Development of Research Technique for Assessing the Water Separation Characteristics of Fuels and Fuel-additive Combinations (CRC Project No. CA- 19-59) September 1961.

This index is a relative measure of the ability of a fuel or a fuel-additive combination to release entrained or emulsified water when passed through a coalescer type water separator.

This index of a fuel is determined with the CRC Water Separometer. This is a small volume apparatus in whcih a water-fuel emulsion is prepared and metered through a cell containing a standardized Fiberglas coalescer. The effluent is analyzed for entrained water by light transmission. A numerical scale rates the ease with which a given fuel releases the dispersed or emulsified water; the higher the numerical rating on the Water Separation Index (0- 100), the better the separation that is achieved. The test used on these compositions is the WSIM test, which is the military modification of the WSI test. The WSIM test is much more severe by a factor of about 15, and is presently used by all laboratories to evaluate the water separation characteristics of fuels and fuel-additive combinations.

CORROSION TEST Refinery stream overhead conditions are simulated in a laboratory bench scale apparatus. The test atmosphere consists of hydrocarbon, low solids water and nitrogenair-hydrogen sulfide gases. Corrosion rates are determined by weight differences that result from exposing a mild steel coupon in this atmosphere for eighteen hours. V

The procedure consists of adding 425 cc. of depolarized naphtha and 22.5 cc. of refinery stream water and the inhibitor to a 1000 ml. round bottom three neck Pyrex flask. The gas tube-coupon holder is inserted into the flask neck and the flow of gas started.

The gas tube-coupon holder is inserted into the flask neck and the flow of gas started. The cone drive motor is turned on as is the heating mantle (if required). The test is allowed to run for an hour before'the coupon is inserted to attain equilibrium. The coupon is positioned such that the gas dispersion tube is on the down stream side of the coupon, the gas makes a complete circuit of the flask before it hits the coupon;

At the end of the test, which usually runs overnight, the coupon is removed from the flask, cleaned with cleansing powder to remove loose corrosion products, dipped with agitation in an inhibited acid bath for thirty seconds, in a saturated soda ash bath for twenty seconds, washed in tap water to remove remaining salts, dipped with agitation in an acetone bath and spun dry. The coupon is then dried in a C. oven for thirty minutes and reweighed. Corrosion rates can be determined on a basis of coupon size and test duration, however for corrosion inhibitor evaluation purposes, the weight loss for treated tests are compared with weight losses from untreated tests at equivalent pHs.

PHOSPHORYLATION phorous yields pure products, but also yields hydrochloric acid which would .be difficult arid expensive to remove from the formulation, would be corrosive to the reactor,

and in addition would represent a loss of product, thus increasing chemical costs considerably. The anhydride, or

phosphorous pentoxide does not present any of the above problems and based on the technology developed represents the most economical source of phosphorousfor the development of the desired product. Its only drawback is that to'maintain the quality .of the final products, decomposition of the anhydride by contact with moisture must be avoided. The phosphorylated bis-propanols, their salts and combinations can be-easily prepared.

The just recited compounds may be formed via a number of known synthetic routes. However, the preferred mode of preparation involves sequential reaction of phosphorous pentoxide andthe bis-propanol followed by reaction with an alcohol. From this synthesis a mixture of products are produced. Partial or complete reaction can occur dependent on the reactants, ratio of reactants, and reaction conditions. Preferably, there is a complete reaction to form the' phosphorylated bis-propanols and phosphorous derivatives.

The products formed were prepared in the laboratory by forming an ether-pentoxide slurry in a nitrogen blanketed reactor, followed by the slow addition of the bis-propanols. In the plant, the products were prepared in a hexane-kerosene slurry. (Ether is too dangerous in plant production.

Initial reaction is exothermic and temperatures were maintained between 7083 C. This reaction mix was stirred at this temperature and then cooled to 40 C. after which the alcohol was added slowly (exothermic reaction) and stirred at temperatures not exceeding 110 C. for from 3 to 5 hours.

An alcohol having at least four carbon atoms could be used, with iso-octyl alcohol being the preferred alcohol.

The reaction mechanism consists of one mole of bispropanol reacted with one mole of phosphorous pentoxide. The ring structure of the phosphorous pentoxide is opened by this reaction. Then, five moles of an alcohol, preferably iso-octyl alcohol react to form phosphorylated bis-propanols and alkyl phosphonic acid. Preferably, the ratio of bis-propanol to phosphorous pentoxide to iso- 10 An example of the phosphorylation is given in Example II.

EXAMPLE II To a clean, dry, and nitrogen blanketed 100 gallon stainless steel reactor provided with an efiicient stirring and a water cooling steam-heating jacket, is charged the following: 130.5 pounds kerosene, clear and bright; 60.0 pounds phosphorous pentoxide with rapid and eflicient stirring. The slurry which is formed must suspend all of the phosphorous pentoxide as fine particles. To this dis persion is added slowly, 40.2 pounds of Formulation 12 from Table I, which is a bis-propanol of a primary amine having from 12-18 carbon atoms in chain length. Formulation 12 is added in small portions, such that a temperature of 100 C. is not exceeded until all of the amine has been added.

The reaction mix is stirred for 1 to 1% hours at 100 C., maintaining a nitrogen atmosphere throughout the process, preferentially at pressures slightly greater than atmospheric. After this time period, the reaction mix is cooled to 40 C. and 137.5 pounds of isooctanol is added slowly, maintaining the temperature during addition at from 40-50 C. with cooling as needed to maintain this temperature range. After the isooctanol addition, the mixture is heated to 100-105 C. for 2 to 2% hours. The solution should be clear at this point. If it is not clear, it will be necessary to cool to room temperature 25 35 C. and filter through a dried filter precoated with Celite. If clarification occurs, simple filtration at 25 35 C. will be satisfactory.

Kerosene is added in the quantity necessary to bring the final active composition to 50.0 weight percent. This final product is then stored in lined drums. An amine can be added to the final product to adjust the product to any required or preferred pH.

Similar products were prepared using the formulations of Table I.

Samples of the product produced according to Example I was labeled Formulation IX, and samples of the products, produced according to Example 11 was labeled Formulation 2X.

The solubility of Formulation 1X (bis-propanols) and Formulation 2X (phosphorylated bis-propanols) is given in the following table. These formulations are discussed subsequently.

TABLE II.SOLUBILITY IN VARIOUS HYDROCARBON FRACTIONS Solvent 20% active active 20% active 60% active Mineral seal oil No visible insol. in the 5,000- No visible insol. in the 5,000- N o visible insol. in the 5,000- No visible insol. in the 5, 000- 5 p.p.m. range. 5 p.p.m. range. 5 p.p.m. range. 5 p.p.m. range.

Kerosene do do do Do.

Naphtha do Do.

Aromatic solvent do Do.

(It-624). Heptane do Do. Butane 2 do do do Do.

1 At 80 F., in all solvents except butane.

2 Above 1% in butane, a haze is evident. Below 1% this cloud is not visible.

octyl alcohol is 1:1:5 but other ratios, such as 122:4 have been used and found to produce comparative products. The reaction should be run in a temperature range between 80-180 C.

Because it was realized that the synthesis of the phosphorylated bis-propanols in ether may preclude manufacture in current plant equipment, use of kerosene as a carrier of the pentoxide was studied. Using approximately the same procedure as above, excluding the stripping step, products of quality and performance comparable to those produced in ether were obtained.

TABLE III Water separometer index, military (p.p.m.)

Corrosion inhibition (p.p.m.) Corrosion inhibition (p.p.m.) pH 4.5, F. pH 7.6, 80 F.

Formulation I. 0 2. 5 5. 0 10 15 25 0. 5 V 1. 0 2. 5 5. 0 0. 25 0. 5 1. 0 2. 5

I claim:

1. A non-corrosive hydrocarbon oil composition consisting of liquid hydrocarbon fuels or lubricating oils containing 0.01-100 ppm. of the reaction product of:

(A) bis (1,3-substituted amino) propan-Z-ols having the general formula:

wherein R is a radical independently selected from the group consisting of hydrogen, hydrocarbons and substituted hydrocarbons having from 1-36 carbon atoms and is alkyl, aryl, alkaryl, alkenyl, acyl, oxyalkyl, fl-cyanoethyl, alkylene aziridinyl, alicyclic and polyoxyalkenyl;

(B) phosphorous pentoxide; and

(C) iso-octyl alcohol; the reaction of said composition in a ratio of 1:1:5 or 1:2:4 at from 80-180 C.

References Cited UNITED STATES PATENTS Chenicek' 44-'72 Lytle 252392 X Brennan 25251.5 X

Pollitzer 4472 Cyba 4472 X Pollitzer 4472 X Cherbuliez et a1. 260944 X Quanstrom 252392 X Rosenwald' 4472 DANIEL E. WYMAN, Primary Examiner 15 W. I. SHINE, Assistant Examiner US. Cl. X.R. 

